CN1886431B - Hyperbranched polymer - Google Patents
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- CN1886431B CN1886431B CN200480034676.7A CN200480034676A CN1886431B CN 1886431 B CN1886431 B CN 1886431B CN 200480034676 A CN200480034676 A CN 200480034676A CN 1886431 B CN1886431 B CN 1886431B
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- XANDUBQZNQREMK-UHFFFAOYSA-N CC(C)(C(OCC(COC(C(C)=C)=O)OC(C(C)(C)Br)=O)=O)Br Chemical compound CC(C)(C(OCC(COC(C(C)=C)=O)OC(C(C)(C)Br)=O)=O)Br XANDUBQZNQREMK-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(CCCC(C)(*)C1)CCC1(*)N Chemical compound CC(C)(CCCC(C)(*)C1)CCC1(*)N 0.000 description 1
- INIJFQRLRIGKCX-UHFFFAOYSA-N CC(C1C(c2c3c(C)ccc2C)=O)=CC=CC1C3=O Chemical compound CC(C1C(c2c3c(C)ccc2C)=O)=CC=CC1C3=O INIJFQRLRIGKCX-UHFFFAOYSA-N 0.000 description 1
- ZRLDBDZSLLGDOX-UHFFFAOYSA-N Cc1c(C)[o]c(C)n1 Chemical compound Cc1c(C)[o]c(C)n1 ZRLDBDZSLLGDOX-UHFFFAOYSA-N 0.000 description 1
- OMFZAUHFMJDLKI-UHFFFAOYSA-N Cc1nc(c(C)ccc2C)c2[nH]1 Chemical compound Cc1nc(c(C)ccc2C)c2[nH]1 OMFZAUHFMJDLKI-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
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- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/16—Halogens
- C08F12/18—Chlorine
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/18—Chlorine
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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Abstract
The aim of the present invention is to provide a multi-branched polymer, in which branch terminals can be easily modified and which have a high degree of branching and narrow dispersion. By polymerizing a compound having 2 or more polymerization-initiation sites and polymerizable unsaturated bonds with a living radical polymerization method using a metal catalyst, it is possible to produce a multi-branched polymer with narrow dispersion and a high degree of branching and having repeating units represented by the formula (I): wherein R 1 to R 3 each independently represents hydrogen or a hydrocarbon group, R 1 may be bonded to R 3 to form a ring; X represents a connecting group having a valence of 3 or higher; Y may be the same or different and each represents a functional group which may have a halogen atom at a terminal thereof; and a is an integer of 2 or larger.
Description
Technical field
The present invention relates to novel hyperbranched polymer and super multibranched polymer, more specifically, the modification that relates to chain end is easy, (disperseing narrow) that branching index is high and dispersity is low novel hyperbranched polymer and super multibranched polymer.
Background technology
Super multibranched polymer is the polymer with dendrimer similar.Although this polymer has and the similar chemical property of dendrimer and physical property, compare with dendrimer, owing to can easyly synthesizing, thereby receive publicity in recent years.
In the past, as super multibranched polymer, relevant for the several reports example with the super multibranched polymer of polystyrene structure, known by monomer, make its band respond starting point can synthesize the super hyperbranched polymer of object (with reference to Macromolecules,
29, 1079 (1996), J.Polym.Sci., Part A:Polym.Chem.,
36, 955 (1998)).
Yet the super multibranched polymer of recording may not easily be controlled molecular weight or dispersity, when particularly branching index improves, can only obtain the polymkeric substance that dispersity is large in these documents.
Therefore, people seek, by the ratio of control branching, molecular weight, shape etc., to develop the super multibranched polymer with excellent physical characteristic.
In addition, have the report example of the super higly branched chain polyacrylic ester synthesis method that has adopted ATRP method (atom freedom of movement base polymerization), example have AB type Acrylic Acid Monomer active free radical polymerization (with reference to Macromolecules,
30, 5192 (1997)).Provide with AB
*type Acrylic Acid Monomer is as the super multibranched polymer of polymerization starting point, and the structure of the super multibranched polymer obtaining does not have symmetry, is not the so-called material with star polymer characteristic.With AB
2the knowledge that type Acrylic Acid Monomer is relevant is not disclosed.
Summary of the invention
Practical situation in view of described conventional art, have completed the present invention.Problem of the present invention is to provide the structural symmetry of super multibranched polymer good, a modification chain end is easy, branching index is high and disperse narrow hyperbranched polymer.
In order to solve above-mentioned problem, the processes such as the inventor study intensively, found that: by employing used the living radical polymerization polymerization of metal catalyst have 2 or more poly close the compound of initial point and polymerizability unsaturated link(age), the modification that can easily obtain chain end is easy, branching index is high and disperse narrow hyperbranched polymer, thereby has completed the present invention.
That is, the invention provides following polymkeric substance,
(1) hyperbranched polymer, is characterized in that, has the repeating unit representing by formula (I),
Described formula (I) is
In formula (I), R
1～R
3independent separately, represent hydrogen atom or alkyl, R
1and R
3can be in conjunction with forming ring, X represents 3 valencys or link group more at high price.Y represents to have the functional group of reactive halogen atom, and a represents 2 or larger integer, between Y, can be the same or different.
(2) as the hyperbranched polymer of above-mentioned (1), it is characterized in that, is the repeating unit representing by formula (II) with the repeating unit that above-mentioned formula (I) represents,
Described formula (II) is
In formula (II), R
1～R
3represent the meaning same as described above, Z represents singly-bound or divalent or link group more at high price, and A represents aromatic hydrocarbyl or aromatic heterocyclic group.R
4expression can have the functional group of reactive halogen atom, and b represents 2 or larger integer, R
4between can be the same or different.R
5represent halogen atom or organic group, d represents 0 or 1 or larger integer, and d is 2 or when larger, R
5between can be the same or different.
(3) as the hyperbranched polymer of above-mentioned (2), in described formula (II), Z is singly-bound, and A is aromatic hydrocarbyl, R
4for the functional group representing by formula (III),
Described formula (III) is
In formula (III), R
6, R
7independent separately, to represent hydrogen atom, halogen atom, can there is substituent alkyl or represent to combine with other repeating unit combination hand (in conjunction with hand).But, R
6, R
7can not become the combination hand combining with other repeating unit simultaneously.
(4) hyperbranched polymer as described in (1), is characterized in that, is the repeating unit representing by formula (IV) with the repeating unit that above-mentioned formula (I) represents,
Described formula (IV) is
In formula (IV), R
1～R
3, Y and a represent the meaning same as described above, V represents 3 valencys or the link group of high price more.
(5) hyperbranched polymer as described in (4), is characterized in that, in above-mentioned formula (IV), V is alkylene polyoxy.
(6) hyperbranched polymer as described in (4) or (5), is characterized in that, in above-mentioned formula (IV), Y is the functional group representing by formula (V),
Described formula (V) is
In formula (V), R
61, R
71independent separately, to represent hydrogen atom, halogen atom, can there is substituent alkyl or represent to combine with other repeating unit combination hand.But, R
61, R
71can not become the combination hand of other repeating unit simultaneously.
(7) hyperbranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to obtain with the compound polymerization that formula (VI) represents,
Described formula (VI) is
In formula (VI), R
8～R
10independent separately, represent hydrogen atom or alkyl, R
8and R
10can be in conjunction with forming ring, X
1represent 3 valencys or link group more at high price.Y
1expression can have the functional group of reactive halogen atom, and a1 represents 2 or larger integer, Y
1between can be the same or different.R
11represent chlorine atom, bromine atoms or iodine atom.
(8) hyperbranched polymer as described in (7), is characterized in that, is the compound representing by formula (VII) with the compound that above-mentioned formula (VI) represents,
Described formula (VII) is
In formula (VII), R
8～R
10represent the meaning same as described above, Z
1represent singly-bound or divalent or link group more at high price, A1 represents aromatic hydrocarbyl or aromatic heterocyclic group.R
24expression can have the functional group of reactive halogen atom, and b1 represents 2 or larger integer, R
24between can be the same or different.R
25represent halogen atom or organic group, d1 represents 0 or 1 or larger integer, and d1 is 2 or when larger, R
25between can be the same or different.R
26represent chlorine atom, bromine atoms or iodine atom.
(9) hyperbranched polymer as described in (8), is characterized in that, in above-mentioned formula (VII), and Z
1for singly-bound, A1 is aromatic hydrocarbyl, R
24the functional group representing by formula (VIII),
Described formula (VIII) is
In formula (VIII), R
60, R
70independent separately, represent hydrogen atom, halogen atom or can there is substituent C1～C6 alkyl.But, R
60, R
70can not become fluorine atom halogen atom in addition simultaneously.
(10) hyperbranched polymer as described in (7), is characterized in that, is the compound representing by formula (IX) with the compound that above-mentioned formula (VI) represents,
Described formula (IX) is
In formula (IX), R
8～R
10represent respectively the meaning same as described above, V
11represent 3 valencys or link group more at high price, Y
1expression can have the functional group of reactive halogen atom, and a1 represents 2 or larger integer, Y
1between can be the same or different.R
11represent chlorine atom, bromine atoms or iodine atom.
(11) hyperbranched polymer as described in (10), is characterized in that, in above-mentioned formula (IX), and V
11it is alkylene polyoxy.
(12) hyperbranched polymer as described in any one in (10) or (11), is characterized in that, in above-mentioned formula (IX), and Y
1the functional group representing by formula (X),
Described formula (X) is
In formula (X), R
610, R
710independent separately, to represent hydrogen atom, halogen atom, can there is substituent alkyl or represent to combine with other repeating unit combination hand.But, R
610, R
710can not become the combination hand of other repeating unit simultaneously.
(13) as any hyperbranched polymer in above-mentioned (1)～(12), it is characterized in that, the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.01～9.99.
(14) as any hyperbranched polymer in above-mentioned (1)～(13), it is characterized in that the scope that number-average molecular weight (Mn) is 200～20000000.
(15) as any hyperbranched polymer in above-mentioned (1)～(14), it is characterized in that, hyperbranched polymer is super multibranched polymer.
(16) super multibranched polymer, is characterized in that, by C-C, carries out branching, the scope that the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.01～9.99.
(17) super multibranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to make to have 2 or more polymerization starting point and the compound polymerization of polymerizability unsaturated link(age) to obtain.
(18) the super multibranched polymer as described in any one in (16) or (17), is characterized in that, the scope that number-average molecular weight (Mn) is 200～20000000.
(19) super multibranched polymer, is characterized in that, has functional group in polymer ends.
(20) star polymer, is characterized in that, the hyperbranched polymer described in using (1)～any one in (15) or the super multibranched polymer described in any one in (16)～(19) are as core.
Below, describe hyperbranched polymer of the present invention in detail.
1) hyperbranched polymer
(1) hyperbranched polymer
Hyperbranched polymer of the present invention, is characterized in that, has the repeating unit representing by above-mentioned formula (I).
In above-mentioned formula (I), R
1～R
3independent separately, represent hydrogen atom or alkyl.As alkyl, can enumerate the alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl; The cycloalkyl such as cyclopentyl, cyclohexyl; The aromatic bases such as phenyl, 1-naphthyl, 2-naphthyl; The aralkyl such as benzyl etc.There is no particular limitation for the carbonatoms of alkyl, is preferably 1～10.
In addition, R
1and R
3can be in conjunction with forming ring.
X represents 3 valencys or the link group of high price more, so long as have the functional group of 3 or more combination hands, just there is no particular limitation.Specifically exemplify functional group shown below.
In said structure formula, be illustrated in R
3in conjunction with carbon atom on the end of combination.For other, there is no the special structural formula of recording, its binding site does not limit.
Y represents to have the functional group of reactive halogen atom.A represents 2 or larger integer, between Y, can be the same or different.
Therefore " functional group can with reactive halogen atom " refers to, while being combined with halogen atom on the carbon atom forming, described functional group has the structure that this halogen atom becomes reactive halogen atom.Particularly, can example can there is the functional group of halogen atom on the α position of electron-withdrawing groups such as carbonyl, ester group, amide group, alkylsulfonyl, itrile group, nitro etc.
As the halogen atom of combination on Y, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom, preferably chlorine atom, bromine atoms.
As the object lesson of Y, can enumerate following functional group.
In addition, when X is aromatic hydrocarbyl or aromatic heterocyclic group, as Y, example has functional group as follows.
In the present invention, with the repeating unit that described formula (I) represents, be preferably the repeating unit representing by described formula (II).
In described formula (II), R
1～R
3represent the meaning same as described above, Z represents singly-bound or divalent or link group more at high price.
As divalent or the link group of high price more, so long as have the functional group of 2 or more combination hands, just there is no particular limitation, and for example, example has the link group shown in following.
In described formula (II), A represents aromatic hydrocarbyl or aromatic heterocyclic group.
As aromatic hydrocarbyl, can enumerate phenyl, 1-naphthyl, 2-naphthyl, anthryl etc.In addition, as aromatic heterocyclic group, can enumerate pyridine, pyrroles, furans, thiophene,
azoles, different
the aromatic heterocyclic groups such as azoles, imidazoles, pyrazoles, thiazole, isothiazole, indoles, benzoglyoxaline.
R
4be illustrated in the functional group can on end with reactive halogen atom.B represents 2 or larger integer, R
4between can be the same or different.
As R
4object lesson, can enumerate the identical material of material of crossing with example in Y.
R
5represent halogen atom or organic group, d represents 0 or 1 or larger integer.D is 2 or when larger, R
5between can be the same or different, and R
5between also can mutually combine and form ring.
As R
5object lesson, can enumerate the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, iodine atom; The alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, phenyl, naphthyl, benzyl; The alkoxyl group such as methoxyl group, oxyethyl group etc.
The repeating unit more preferably with the repeating unit that described formula (II) represents in the present invention, with following feature: in described formula (II), Z is singly-bound, and A is aromatic hydrocarbyl, R
4for the functional group representing by described formula (III).
In described formula (III), R
6, R
7independent separately, to represent hydrogen atom, halogen atom, can there is substituent alkyl or represent to combine with other repeating unit combination hand.But, R
6, R
7can not become the combination hand combining with other repeating unit simultaneously.
As R
6, R
7halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom etc.As thering is substituent alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, benzyl, trifluoromethyl etc.There is no particular limitation can to have the carbonatoms (moieties) of above-mentioned substituent alkyl, is preferably 1～6.
In addition, while becoming the combination hand of other repeating unit, refer to R
6, R
7in conjunction with carbon as basic point, further make polymeric chain extension.For example, use-CHCl
2while carrying out polymerization in halogenide.
In addition, in the present invention, with the repeating unit that described formula (I) represents, be preferably the repeating unit representing by described formula (IV).
In described formula (IV), R
1～R
3represent the meaning same as described above, V represents 3 valencys or the link group of high price more, so long as have the functional group of 3 or more combination hands, just there is no particular limitation.Specifically can example there be the functional group identical with described X, particularly preferably alkylene polyoxy.
As alkylene polyoxy, concrete example has the link group shown in following.
In described formula (IV), Y represents the meaning same as described above, and Y is preferably the repeating unit representing by described formula (V).
In described formula (V), R
61and R
71represent and described R
6and R
7the identical meaning, independent separately, so long as represent hydrogen atom, halogen atom, can there is substituent alkyl or the functional group of the combination hand that represents to combine with other repeating unit, with regard to there is no particular limitation.But, R
61, R
71can not become the combination hand of other repeating unit simultaneously.Concrete example has functional group same as described above.
As described formula (I), specifically can enumerate the material shown in following formula.
Although hyperbranched polymer branching index of the present invention is high, dispersity low (disperseing narrow), and easily modify on a chain end, therefore there is the characteristic in the past not having.
There is no particular limitation for the number-average molecular weight of hyperbranched polymer of the present invention (Mn), is preferably 200～20000000 scope.
The ratio (Mw/Mn) of the weight-average molecular weight of hyperbranched polymer of the present invention (Mw) and number-average molecular weight (Mn) is although there is no particular limitation, but preferred 1.01～9.99 scope, more preferably 1.01～5.50 scope, particularly preferably 1.01～2.50 scope.
Hyperbranched polymer of the present invention is preferably super multibranched polymer.The tree-shaped polymer phases such as super multibranched polymer and dendrimer are same, are on side chain, to have side chain, the polymer of the mixture of the repeating unit that contains wire and complete branching.
Hyperbranched polymer of the present invention can be by modifying reactive halogen atomic reaction remaining in molecular end portion.For example, can be by reacting acetylize with acetate.
(2) manufacture of hyperbranched polymer
Manufacture method as hyperbranched polymer of the present invention, so long as can obtain having the high molecular method of the repeating unit representing by described formula (I), just there is no particular limitation, the living radical polymerization that the compound that the described formula (VI) of can preferred exemplary usining represents is used as monomer.By this method, can be easy and the controlled hyperbranched polymer of the present invention of manufacturing structure efficiently.
In described formula (VI), R
8～R
10independent separately, represent hydrogen atom or alkyl, R
8and R
10can be in conjunction with forming ring.As R
8～R
10object lesson, can enumerate with above-mentioned as R
1～R
3the cited identical material of material of object lesson.
X
1represent 3 valencys or link group more at high price, as its object lesson, can enumerate with above-mentioned as the identical material of the cited material of the object lesson of X.
Y
1be illustrated in the functional group that end can have reactive halogen atom, as its object lesson, can enumerate with above-mentioned as the identical material of the cited material of the object lesson of Y.
A1 represents 2 or larger integer, Y
1between can be the same or different.
R
11represent chlorine atom, bromine atoms or iodine atom.
In the present invention, as the compound representing by described formula (VI), preferably use the compound being represented by described formula (VII), (IX).
In described formula (VII), Z
1represent singly-bound or divalent or link group more at high price, as its object lesson, can enumerate with above-mentioned as the identical material of the cited material of the object lesson of Z.
A1 represents aromatic hydrocarbyl or aromatic heterocyclic group, as its object lesson, can enumerate with above-mentioned as the identical material of the cited material of the object lesson of A.
R
24be illustrated in the functional group that end can have reactive halogen atom, b1 represents 2 or larger integer, R
24between can be the same or different.As R
24object lesson, can enumerate with above-mentioned as R
4the cited identical material of material of object lesson.
R
25represent halogen atom or organic group, d1 represents 0 or 1 or larger integer, and d1 is 2 or when larger, R
25between can be the same or different.As R
25object lesson, can enumerate with above-mentioned as R
5the cited identical material of material of object lesson.
R
26represent chlorine atom, bromine atoms or iodine atom.
In the present invention, in the compound representing by described formula (VII), more preferably use the compound with following feature: Z
1for singly-bound, A1 is aromatic hydrocarbyl, R
24for the functional group representing by described formula (VIII).
In described formula (VIII), R
60, R
70independent separately, represent hydrogen atom, halogen atom or can there is substituent C1～C6 alkyl.But, R
60, R
70can not become fluorine atom halogen atom in addition simultaneously.As R
60, R
70object lesson, can enumerate with above-mentioned as R
6, R
7the cited identical material of material of object lesson.
In described formula (IX), V
11identical with described V, represent 3 valencys or link group more at high price, as its object lesson, can enumerate with above-mentioned as the identical material of the cited material of the object lesson of X.
R
8～R
10represent respectively the meaning same as described above, Y
1expression can have the functional group of reactive halogen atom, as R
8～R
10object lesson, can enumerate with above-mentioned as R
1～R
3the cited identical material of material of object lesson.As Y
1concrete example, can enumerate the material identical with material cited in the above-mentioned object lesson as Y.
A1 represents 2 or larger integer, Y
1between can be the same or different.
R
11represent chlorine atom, bromine atoms or iodine atom.
In described formula (X), R
610, R
710independent separately, represent hydrogen atom, halogen atom or can there is substituent C1～C6 alkyl.But, R
610, R
710can not become fluorine atom halogen atom in addition simultaneously.As R
610, R
710object lesson, can enumerate with above-mentioned as R
6, R
7the cited identical material of material of object lesson.
As the object lesson of the compound representing by described formula (VI), can enumerate material as follows.In following structural formula, R
261～R
264independent separately, represent the halogen atoms such as chlorine atom, bromine atoms.
As the object lesson of the compound representing by described formula (IX), can enumerate material as follows.In following structural formula, R
265～R
268independent separately, represent the halogen atoms such as chlorine atom, bromine atoms.
As the catalyzer using, can example there is known metal complex in living radical polymerization.Wherein, can example have, the copper complex of the monovalencies the such as preferably copper complex of monovalence is, the ruthenium complex of the iron complex of divalence, divalence, tellurium complex, and more preferably cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, Red copper oxide, cuprous acetate, perchloric acid be cuprous; The tellurium complexs such as (1-ethoxy carbonyl-1-methylethyl) methyl tellurium, (1-cyano group-1-methylethyl) methyl tellurium, α-methylbenzyl methyl tellurium, benzyl methyl tellurium, methyl benzoyl tellurium.
When using copper compound, as the dentate that improves catalyst activity, can add 2,2 '-bipyridine, 1,10-phenanthroline, alkanamine (Tributylamine etc.), polyamine (Tetramethyl Ethylene Diamine, pentamethyl-ethylidene diethyl triamine, hexamethyl three second tetramines etc.) etc.
The amount of the catalyzer using can be as requested the molecular weight of hyperbranched polymer suitably select, with respect to the monomer using, the preferred scope of 1～50 % by mole, the more preferably scope of 5～45 % by mole, the further preferred scope of 20～40 % by mole.
In living radical polymerization, due to further with transition metal complex effect, thereby as the activator that radical polymerization is promoted, can use known Lewis acid and/or amine.
There is no particular limitation for polymerization process, can adopt common methods such as mass polymerization, solution polymerization, suspension polymerization or emulsion polymerization, wherein, and particularly preferably solution polymerization.
While carrying out solution polymerization, there is no particular limitation for solvent.For example, can use the arenes such as benzene,toluene,xylene; The alicyclic hydrocarbon types such as hexanaphthene; The fat hydrocarbon such as normal hexane, octane; The ketones such as acetone, methyl ethyl ketone, pimelinketone; Tetrahydrofuran (THF), two
the ethers such as alkane; The ester such as ethyl acetate, butylacetate class; The amides such as DMF, N,N-dimethylacetamide; The sulfoxide types such as methyl-sulphoxide; The alcohols such as methyl alcohol, ethanol; The polyol derivative classes such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate etc.
Such solvent can be used separately a kind, or two or more are mixed and are used.
By the compound living radical polymerization polymerization that will represent with described formula (VI), can manufacture hyperbranched polymer of the present invention.As the compound representing by described formula (VI) being carried out to the method for active free radical polymerization, specifically can enumerate following (a)～method (d).
(a) method of the hyperbranched polymer of the homopolymer of the compound that manufacture represents containing useful described formula (VI);
(b) method of the hyperbranched polymer that the compound that interpolation represents by described formula (VI) simultaneously in reaction system and other polymerizability unsaturated monomer manufacture contain random copolymers;
(c) method of the hyperbranched polymer that the compound that interpolation represents by described formula (VI) successively in reaction system and other polymerizability unsaturated monomer manufacture contain random copolymers.
(d) method of the hyperbranched polymer that the compound that interpolation represents by described formula (VI) successively in reaction system and other polymerizability unsaturated monomer manufacture contain gradient copolymer.
Polymerization conventionally can be under the inert gas atmospheres such as vacuum or nitrogen, argon, 0～200 ℃ of temperature, preferably 40～1 50 ℃, further preferably 80～120 ℃, normal pressure or add to depress and carry out.
The tracking of polymerization process and reaction finish really to approve easily carry out by vapor-phase chromatography, liquid phase chromatography, gel permeation chromatography, membrane osmotic pressure method, NMR etc.
After copolyreaction finishes, refining by application chromatographic column, or the component of polymer of separating out after putting in water for example or poor solvent is filtered, make its common separation and refining method such as dry, can obtain multipolymer.
There is no particular limitation for the molecular weight of hyperbranched polymer of the present invention, can exemplify, and number-average molecular weight (Mn) is preferably 200～20000000 scope, further preferably 1000～20000000 scope, 5000～150000 scope.
The ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is although there is no particular limitation, preferably 1.01～9.99 scope, more preferably 1.01～5.50 scope, particularly preferably 1.01～2.50 scope.
In addition, the ratio (Mw/Mn) of number-average molecular weight (Mn), weight-average molecular weight (Mw) and number-average molecular weight (Mn) adopts by multi-angle scattering of light and detects the value that method (being designated hereinafter simply as MALS method) mensuration obtains.
In having the hyperbranched polymer of different shape or proterties, the method for the application of the invention, makes it possible to control molecular weight and manufactures the super multibranched polymer that is in the past considered to be difficult to control molecular weight.That is, can manufacture the super multibranched polymer of the proterties in the past not having.
And then hyperbranched polymer of the present invention utilizes the functional group of its end, can further extend polymer chain, wherein, described end is characterised in that can have the functional group that can be transformed into other functional group on its end.
2) star polymer
Star polymer of the present invention, is characterized in that, usings hyperbranched polymer of the present invention as core.
The star polymer that has adopted hyperbranched polymer of the present invention, is characterized in that, can select arbitrarily the different polymkeric substance of branching index for core, as required, can change arm number.
As the manufacture method of star polymer of the present invention, specifically can example there is following method etc.:
(1) utilize the functional end-group of hyperbranched polymer of the present invention, adopt living radical polymerization to make the method as the polymeric chain extension of arm,
(2) utilize the functional end-group of hyperbranched polymer of the present invention, make itself and the method with the polymer chain reaction of the end that can react with the functional end-group of the hyperbranched polymer of adjusting in advance.While particularly adopting the method shown in (1), from the end of hyperbranched polymer, slowly make polymeric chain extension, therefore can effectively utilize functional end-group, and then the molecular weight of arm polymer chain is consistent owing to making, therefore preferably.
Accompanying drawing explanation
Fig. 1 means the figure of the hyperbranched polymer 1 that obtains in embodiment 1 particle diameter in 2wt% tetrahydrofuran solution.
Embodiment
Use embodiment that the present invention is described in further detail below, but scope of the present invention is not limited to these embodiment.
Embodiment
(synthesis example)
Synthesizing of two (chloromethyl) vinylbenzene (BCMS) of (1) 3,5-
In the reaction vessel of 200ml, by 3,5-two (methoxymethyl) bromobenzene 13.4g (54.7mmol), magnesium 3.25g (134mmol) and tetrahydrofuran (THF) (being designated hereinafter simply as " THF ") 60ml, make Ge Liya solution.Then, at 0 ℃, in this solution, drip dimethyl formamide (DMF) 30ml (387mmol), after dropping finishes, at room temperature further stir 3 hours.Removal of solvent under reduced pressure from the reaction solution obtaining, adds 2N hydrochloric acid.By the reaction mixture obtaining 50ml ether extraction 3 times, collected organic layer, water is dried with anhydrous magnesium sulfate after cleaning.By refining with silica gel column chromatography except the residue obtaining after desolventizing, obtain being the object product 3 of thick liquid, two (methoxymethyl) phenyl aldehyde 8.36g (43.0mmol) of 5-.Yield is 79%.
Then, the THF solution 30ml of two (methoxymethyl) phenyl aldehyde 8.36g (43.0mmol) of 3,5-is added drop-wise to methyltriphenylphospbromide bromide at 0 ℃
in the THF solution 40ml of 18.5g (51.7mmol) and tert.-butoxy potassium 7.24g (64.5mmol).At 0 ℃, stirring reaction liquid, after 3 hours, adds water 30ml, makes remaining tert.-butoxy potassium inactivation.Isolate organic layer, water layer is extracted after 3 times with 50ml ether, collected organic layer, is dried with anhydrous magnesium sulfate.In the residue except obtaining after desolventizing, add normal hexane 80ml, make superfluous methyltriphenylphospbromide bromide
precipitate with triphenyl phosphine oxide.After insolubles filtering separation, the enriched material of filtrate is refined with silica gel column chromatography, obtain being the object product 3 of colorless oil, two (methoxymethyl) vinylbenzene 5.52g (28.7mmol) of 5-.Yield is 67%.
Then, in the reaction vessel of 200ml, two (methoxymethyl) vinylbenzene 2.76g (14.4mmol) of 3,5-are dissolved in 30ml tetracol phenixin, at 0 ℃, drip the dichloromethane solution 40ml of boron trichloride 1.0M, at 0 ℃, further stir 12 hours.In reaction solution, add methyl alcohol, after handling superfluous boron trichloride, gained material is injected into 5%NaOH solution 150ml (being added with 100g ice).Isolate organic layer, with anhydrous magnesium sulfate, be dried.By refining with silica gel column chromatography except the residue obtaining after desolventizing, obtain being the object product 3 of transparent liquid, two (chloromethyl) vinylbenzene 1.57g (7.81mmol) of 5-.Yield is 54%.
(2) 2,3-'s two (the bromo-2-methyl-propionyl of 2-oxygen base-propyl group-2-methyl-acrylate) is synthetic
In the reaction vessel of 500ml, pack glycidyl methacrylate 7.8g (55mmol), 2-isobutyl bromide 18.3g (110mmol) into, drip triethylamine 16.3g (161.4mmol).At 70 ℃, stir 5 hours.Gained solution is cooling, make after it is dissolved in chloroform, with saturated sodium bicarbonate aqueous solution, to clean.Concentrated this extracts solution, uses
1h-NMR confirms the generation of compound.
Then, in this extraction solution, add pyridine 5.94g (75mmol), being cooled to add 2-bromine isobutyl acylbromide 13.8g (60mmol) under the condition of 0 ℃, at room temperature stir and spend the night.Reaction solution is washed with water, with chloroform extraction, after dried over mgso, by the silica gel column chromatography for solution having concentrated (hexane: ethyl acetate=4: 1) carry out separation.Obtain water white transparency viscous compound 22.4g (yield is 89%: the add-on by glycidyl methacrylate converts).
(embodiment 1)
(3) hyperbranched polymer 1 is synthetic
In the reaction vessel of 100ml, be added in above-mentioned (1), obtain 3,5-two (chloromethyl) vinylbenzene 2.28g (11.3mmol), cupric chloride (I) 0.336g (3.40mmol), dipyridyl 1.06g (6.80mmol) and chlorobenzene 12ml, after mixing equably, with current vent fan, make inner degassed.Reaction system is replaced as after nitrogen, and sealed reaction vessel stirs 90 minutes in presetting into the oil bath of 115 ℃.In reaction mixture, add the about 20ml of THF, in air, under room temperature, stir about is 30 minutes.The mixture obtaining is refined with alumina column, by carrying out redeposition with methyl alcohol, obtained the hyperbranched polymer 1 that 1.04g is yellow goo.The weight-average molecular weight of this material, with gel permeation chromatography (being designated hereinafter simply as " GPC method "), press polystyrene conversion, the result of measuring is Mw=3958 (Mw/Mn=1.74), and the result that detects method (being designated hereinafter simply as MALS method) mensuration with multi-angle scattering of light is Mw=14510 (Mw/Mn=1.71).
(4) size distribution of hyperbranched polymer 1 solution
The assay method > of < size distribution
Adopt HPPS (the particle size determination device that MALVERN Inst. company manufactures) to measure particle diameter.
The measurement result > of < particle diameter, size distribution
Median size is respectively 6.2nm (5wt% solution), 7.2nm (2wt% solution), 8.0nm (0.2wt% solution), 6.4nm (0.03wt% solution).In addition, the size distribution of its 2wt% solution is illustrated in Fig. 1.
Similarly, replace tetrahydrofuran solvent and make 2wt% solution with toluene, hexane, acetone, dimethyl methyl imide, chloroform, its median size is 7nm, thereby thinks and be not subject to the impact of solvent.
In addition, as shown in Figure 1, the solution of hyperbranched polymer 1 contains the nanoparticle with transparent single dispersion size distribution.
(embodiment 2)
(5) hyperbranched polymer 2 is synthetic
In the reaction vessel of 100ml, be added in monomer 2.10g (4.58mmol), cupric bromide (I) 0.197g (1.37mmol), dipyridyl 0.43g (2.75mmol) and the chlorobenzene 7.9g that in above-mentioned (2), obtain, after mixing equably, with current vent fan, make inner degassed.Reaction system is replaced as after nitrogen, and sealed reaction vessel stirs 90 minutes in presetting into the oil bath of 110 ℃.With tetrahydrofuran (THF) (THF) solvent, the mixture obtaining is refining with silica gel column chromatography, with hexane, the solution having concentrated is carried out to redeposition 2 times.Obtained the hyperbranched polymer 2 (yield is 32%) that 0.68g is water white transparency viscous compound.The weight-average molecular weight of this material, with " GPC method ", by polystyrene conversion, the result of mensuration is Mw=9640 (Mw/Mn=1.18), by the result that " MALS method " measured, is Mw=5144 (Mw/Mn=1.16).
(embodiment 3)
(6) use the modification (synthesizing of hyperbranched polymer 3) of the hyperbranched polymer of polymeric arms
In the 200ml reaction vessel replacing at nitrogen, add toluene 53g and THF5.4g, be cooled to-40 ℃.Slowly drip wherein n-Butyl Lithium/hexane solution (1.61mol/l) 3.2g, and then add tert.-butoxy vinylbenzene 10.0g (56.7mmol), carry out active anionic polymerization.
Confirm the consumption of monomer by gas-chromatography (GC) after, sample, by GPC method, confirm to have obtained the polymkeric substance of Mn=3903 (Mw/Mn=1.16).
In reaction solution, add the toluene solution 5ml that is dissolved with hyperbranched polymer (hyperbranched polymer 1) 0.5g obtaining in embodiment 1, at-40 ℃, make its reaction 30 minutes.In reaction solution, add methyl alcohol (MeOH), reaction is stopped, by making its redeposition, obtain the faint yellow solid (hyperbranched polymer 2) of 8.70g.The weight-average molecular weight Mw=112000 of the hyperbranched polymer 2 obtaining, Mw/Mn=1.19.
(embodiment 4)
(7) functional group of hyperbranched polymer conversion (synthesizing of hyperbranched polymer 4)
In the reaction vessel of 100ml, be added in the synthetic hyperbranched polymer of embodiment 2 (hyperbranched polymer 2) 0.5g, Potassium ethanoate 1.96g (20.0mmol), Tetrabutyl amonium bromide 0.20g (0.6mmol), acetic acid 0.1ml, water 6.0ml and chlorobenzene 10ml, entire contents is stirred 5 days at 80 ℃.
By reaction mixture separatory, isolate organic layer.By making organic layer redeposition, obtain the Sandy goo (hyperbranched polymer 3) of 0.7g.The weight-average molecular weight Mw=16510 of the hyperbranched polymer 3 obtaining.And, by
1h-NMR measures, and confirms that the transformation efficiency reacting with ethanoyl is 80%.
Industrial applicability
As mentioned above, although hyperbranched polymer branching index of the present invention is high, because dispersity is little, and easily modify at branching end, therefore there is the characteristic in the past not having.
And hyperbranched polymer of the present invention is easily according to utilizing the modification of polymeric arms, the objects such as functional group's conversion of branched chain end are carried out multiple expansion.
Hyperbranched polymer of the present invention can be widely used in the hardening resins such as etchant resist, China ink, coating, electric and electronic material, sealing agent, pleurodiaphragmatic in terspace material or various additives etc. and require to control in the molecular designing of nano-scale structure, can say in industrial using value high.
Claims (14)
1. hyperbranched polymer, is characterized in that, has the repeating unit representing by formula (I),
Described formula (I) is
In formula (I), R
1～R
3independent separately, represent hydrogen atom or alkyl, R
1and R
3in conjunction with forming ring or not forming ring, X represents 3 valencys or link group more at high price, is selected from following group;
Wherein, be illustrated in R
3in conjunction with carbon atom on the end of combination,
Y represents to be selected from the functional group can with reactive halogen atom of following group;
A represents 2 or larger integer, identical or different between Y.
2. hyperbranched polymer, is characterized in that, has the repeating unit representing by formula (II),
Described formula (II) is
In formula (II), R
1～R
3independent separately, represent hydrogen atom or alkyl, R
1and R
3in conjunction with forming ring or not forming ring, Z represents singly-bound or divalent or link group more at high price, and wherein divalent or link group are more at high price selected from following group,
A represents aromatic hydrocarbyl or aromatic heterocyclic group; R
4represent to be selected from the functional group can endways with reactive halogen atom of following group;
B represents 2 or larger integer, R
4between identical or different;
R
5represent halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, phenyl, naphthyl, benzyl, methoxy or ethoxy;
D represents O or 1 or larger integer, and d is 2 or during larger integer, R
5between identical or different.
3. hyperbranched polymer as claimed in claim 2, is characterized in that, in described formula (II), Z is singly-bound, and A is aromatic hydrocarbyl.
4. hyperbranched polymer, is characterized in that, has the repeating unit representing by formula (IV),
Described formula (IV) is
In formula (IV), R
1～R
3independent separately, represent hydrogen atom or alkyl, R
1and R
3in conjunction with forming ring or not forming ring, a represents 2 or larger integer, and V represents 3 valencys or the link group of high price more, is selected from following group,
Wherein, be illustrated in R
3in conjunction with the combination of carbon atom institute-Sauerstoffatom of C=O-O-on the end of combination,
Y represents to be selected from the functional group can with reactive halogen atom of following group;
5. hyperbranched polymer, is characterized in that, has the repeating unit representing by formula (IV),
Described formula (IV) is
In formula (IV), R
1～R
3independent separately, represent hydrogen atom or alkyl, R
1and R
3in conjunction with forming ring or not forming ring, a represents 2 or larger integer, and V represents 3 valencys or the link group of high price more, is selected from following group,
Y represents to be selected from the functional group can with reactive halogen atom of following group;
6. hyperbranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to obtain with the compound polymerization that formula (VI) represents,
Described formula (VI) is
In formula (VI), R
8～R
10independent separately, represent hydrogen atom or alkyl, R
8and R
10in conjunction with forming ring or not forming ring, X
1represent 3 valencys or link group more at high price, be selected from following radicals;
Y
1represent to be selected from the functional group can with reactive halogen atom of following radicals;
A1 represents 2 or larger integer, Y
1between identical or different; R
11represent chlorine atom, bromine atoms or iodine atom.
7. hyperbranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to obtain with the compound polymerization that formula (VII) represents,
Described formula (VII) is
In formula (VII), R
8～R
10independent separately, represent hydrogen atom or alkyl, R
8and R
10in conjunction with forming ring or not forming ring, Z
1represent singly-bound or divalent or link group more at high price, wherein divalent or link group are more at high price selected from following group,
A1 represents aromatic hydrocarbyl or aromatic heterocyclic group; R
24represent to be selected from the functional group can endways with reactive halogen atom of following group;
B1 represents 2 or larger integer, R
24between identical or different;
R
25represent halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclohexyl, phenyl, naphthyl, benzyl, methoxy or ethoxy;
D1 represents 0 or 1 or larger integer, and d1 is 2 or when larger, R
25between identical or different; R
26represent chlorine atom, bromine atoms or iodine atom.
8. hyperbranched polymer as claimed in claim 7, is characterized in that, Z in described formula (VII)
1for singly-bound, A1 is aromatic hydrocarbyl.
9. hyperbranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to obtain with the compound polymerization that formula (IX) represents,
Described formula (IX) is
In formula (IX), R
8～R
10independent separately, represent hydrogen atom or alkyl, R
8and R
10in conjunction with forming ring or not forming ring, V
11represent 3 valencys or link group more at high price, be selected from following group;
Wherein, be illustrated in R
10in conjunction with the combination of carbon atom institute-Sauerstoffatom of C=O-O-on the end of combination,
Y
1represent to be selected from the functional group can with reactive halogen atom of following group;
A1 represents 2 or larger integer, Y
1between identical or different; R
11represent chlorine atom, bromine atoms or iodine atom.
10. hyperbranched polymer, is characterized in that, it is by having used the living radical polymerization of metal catalyst to obtain with the compound polymerization that formula (IX) represents,
Described formula (IX) is
In formula (IX), R
8～R
11independent separately, represent hydrogen atom or alkyl, R
8and R
10in conjunction with forming ring or not forming ring, a1 represents 2 or larger integer, V
11represent 3 valencys or link group more at high price, be selected from following group,
Y
1represent to be selected from the functional group can with reactive halogen atom of following group;
11. hyperbranched polymers as described in any one in claim 1～10, is characterized in that the scope that the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn is 1.01～9.99.
12. hyperbranched polymers as described in any one in claim 1～2,4～7,9～10, is characterized in that the scope that number-average molecular weight Mn is 200～20000000.
13. hyperbranched polymers as described in any one in claim 1～2,4～7,9～10, is characterized in that, hyperbranched polymer is super multibranched polymer.
14. star polymers, is characterized in that, the hyperbranched polymer described in any one of usining in claim 1～2,4～7,9～10 is as core.
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| JP2003394867 | 2003-11-26 | ||
| JP394867/2003 | 2003-11-26 | ||
| PCT/JP2004/017897 WO2005052009A1 (en) | 2003-11-26 | 2004-11-25 | Novel hyperbranched polymer |
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| EP (1) | EP1688440B1 (en) |
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| EP1367080A1 (en) | 2002-05-29 | 2003-12-03 | Hycail B.V. | Hyperbranched poly(hydroxycarboxylic acid) polymers |
| KR20070119097A (en) * | 2003-11-26 | 2007-12-18 | 닛뽕소다 가부시키가이샤 | Novel multi-branched polymer |
| US8153744B2 (en) | 2006-09-07 | 2012-04-10 | Nissan Chemical Industries, Ltd. | Hyperbranched polymer and process for production thereof |
| CA2665607C (en) | 2006-10-04 | 2014-12-02 | University Of Akron | Synthesis of inimers and hyperbranched polymers |
| JP6833485B2 (en) * | 2016-12-05 | 2021-02-24 | 大日精化工業株式会社 | How to make a star polymer, a star polymer, and a filler dispersion |
| JP6924434B2 (en) | 2017-03-02 | 2021-08-25 | 国立大学法人京都大学 | Graft Polymer Initiator |
| US11981777B2 (en) | 2018-08-20 | 2024-05-14 | The University Of Akron | Synthesis of hyperbranched polymethacrylates and polyacrylates by a haloinimer approach |
| WO2020142144A1 (en) * | 2019-01-04 | 2020-07-09 | Carbon, Inc. | Additively manufactured products having a matte surface finish |
| CN115057961B (en) * | 2022-01-04 | 2024-01-26 | 浙江新力新材料股份有限公司 | Hyperbranched polymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5102966A (en) * | 1990-06-14 | 1992-04-07 | Sekisui Chemical Co., Ltd. | Process for preparing star compounds |
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| JPH082923B2 (en) | 1990-06-14 | 1996-01-17 | 積水化学工業株式会社 | Method for producing star compound |
| JP3112711B2 (en) * | 1991-08-12 | 2000-11-27 | 積水化学工業株式会社 | Alkenyl ether compounds and uses thereof |
| US5763548A (en) * | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
| JP4183293B2 (en) * | 1997-07-09 | 2008-11-19 | 日本曹達株式会社 | (Meth) acrylic acid ester polymer and production method thereof |
| US6255424B1 (en) * | 1997-11-25 | 2001-07-03 | Colorado School Of Mines | Dendritic polymers and convergent method of synthesis |
| JP4420152B2 (en) * | 1999-03-26 | 2010-02-24 | 信越化学工業株式会社 | Polymer compound and production method thereof |
| US6414101B1 (en) | 1999-03-26 | 2002-07-02 | Shin-Etsu Chemical Co., Ltd. | Dendritic polymers and making method |
| DE60031280T2 (en) | 1999-08-31 | 2007-01-25 | Nippon Soda Co. Ltd. | star block copolymer |
| JP4623690B2 (en) | 1999-08-31 | 2011-02-02 | 日本曹達株式会社 | Star block copolymer |
| JP4491103B2 (en) | 1999-12-27 | 2010-06-30 | 株式会社Ｋｒｉ | Multi-branched polymer, production method thereof, solid electrolyte and electrochemical device |
| JP4288445B2 (en) * | 2000-10-23 | 2009-07-01 | 信越化学工業株式会社 | Novel onium salt, photoacid generator for resist material, resist material and pattern forming method |
| JP4116788B2 (en) | 2000-11-21 | 2008-07-09 | 日本曹達株式会社 | Star polymers and polyelectrolytes |
| JP3946080B2 (en) * | 2001-05-01 | 2007-07-18 | 株式会社クラレ | Thermoplastic elastomer composition |
| US6639032B2 (en) * | 2001-11-28 | 2003-10-28 | Eastman Kodak Company | Highly branched polymer from telomerization |
| KR20070119097A (en) * | 2003-11-26 | 2007-12-18 | 닛뽕소다 가부시키가이샤 | Novel multi-branched polymer |
-
2004
- 2004-11-25 KR KR1020077027726A patent/KR20070119097A/en not_active Application Discontinuation
- 2004-11-25 KR KR1020067010615A patent/KR100814315B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102966A (en) * | 1990-06-14 | 1992-04-07 | Sekisui Chemical Co., Ltd. | Process for preparing star compounds |
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| JP5600467B2 (en) | 2014-10-01 |
| CN102775535B (en) | 2014-08-27 |
| EP1688440A1 (en) | 2006-08-09 |
| EP1688440A4 (en) | 2009-01-21 |
| JP2010209340A (en) | 2010-09-24 |
| WO2005052009A1 (en) | 2005-06-09 |
| JPWO2005052009A1 (en) | 2007-06-21 |
| EP1688440B1 (en) | 2014-01-01 |
| KR20070119097A (en) | 2007-12-18 |
| US20070142504A1 (en) | 2007-06-21 |
| CN1886431A (en) | 2006-12-27 |
| KR100814315B1 (en) | 2008-03-18 |
| US7732549B2 (en) | 2010-06-08 |
| CN102775535A (en) | 2012-11-14 |
| KR20060093346A (en) | 2006-08-24 |
| JP5101816B2 (en) | 2012-12-19 |
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